Organosilicon compound



Patented July 4, 1944 OBGANOSILICON COMPOUND Eugene G. Rochow, West Albany, N. Y., assignor to General Electric Company, a corporation of New York No Drawing. Application April 30, 1940,

- Serial No. 332,606

8 Claims.

This invention relates to new compositions of matter and, more particularly, to new and useful organo-silicon compounds. Specifically the invention is concerned with the production of organo-silicon compounds in which a plurality of divalent organic radicals are each linked to two separate (diflerent) silicon atoms.

Compounds of silicon, oxygen and divalent organic radicals heretofore have been known. Bygdn (Berichte, 48, 1236, 1915 and Dissertation Upsala, 1916, 105-107) prepared pentamethylene silicone, [(CHz) 5SiO]=, by hydrolysis of pentamethylene silicon di-chloride to the corresponding silicol which, when dehydrated, yielded the silicone. This material is a substituted silicon oxide and. is solid and polymeric by virtue of the --Sl--OSi-'O- network. In polymeric pentamethylene silicone, the pentamethylene radicals are attached to the silicon atoms in this manner:

-o si----0-----si --o---s1 (7H1 CH1 C CH: C CH1 OH; on. on, H1 H1 H,

CH: CHI CH: As will be seen from the above formula, each divalent pentamethylene radical is attached toa single silicon atom.

In marked contrast with the known pentamethylene silicone, the new compounds of this invention are polymeric bodies in which a large number of silicon atoms are linked to one another by divalent (double-ended) organic radicals in this manner:

In the above formula, which for purpose oi clarity has been shown as a doubling of the unit structure,

R represents any divalent organic radical capable of being linked through each of its two valencies to separate silicon atoms. For instance, when R in Formula A represents a divalent aromatic hydrocarbon radical, specifically a phenylene radical, the polymers of this invention con tain the structure The formula designated as (C) also may be written as loHa tHl Similarly, when R in Formula A represents a saturated aliphatic radical such as a methylene or polymethylene radical, specifically -CH2, the polymers of this invention contain the structure lih (EH:

--CHr-|i-CH:-|l etc. Illustrative examples of other divalent organic radicals which R in Formulas A and B may be are dimethylene, -(CH2)2-, trimethylene, (CI-Iz) 3-, tetramethylene, --(CH2)4, pentamethylene, -(CH:) 5--, hexamethylene,

the aliphatic branched chain radicals, for instance methyl methylene,

dimethyl methylene, C(CH3)2-, 2,3 dimethyl tetramethylene,

CHI CH1 CH:-JJH-( JH-CHretc.; alkyl-substituted aryl radicals, e. g., substituted phenylene radicals of the general type,

-CsH3R', where R. is any alkyl or aralkyl substituent radicals; aryl-substituted alkyl radicals, e. g., substituted radicals of the general type,

where R" is any aryl or arkaryl radical. More specific examples of radicals which R and B" may be are given hereafter with particular reference to monovalent organic radicals.

In the polymeric bodies described by Formula A the divalent organic radicals designated generally as R need not all be the same. For example one R may be --(CH2) and another It may be an aliphatic branched chain divalent radical, e. g., methyl methylene, a substituted or unsubstituted phenylene radical, a polymethylene radical, etc. A more specific example of this type of compound is one containing approximately an qual number of pentamethylene and phenylene radicals bonded to silicon atoms. In such a polymer the silicon atoms and divalent organic radicals are bonded together in the inilowing random manner:

I sHc H4 I .5310

By introducing dii'ierent divalent organic radicals into the organo-silicon compounds of this invention, the properties of the polymeric body may be altered as desired or as conditions may require.

Organo-silicon compounds consisting of a plu- I rality of monovalent and divalent organic radicals linked to silicon atoms also may be produced in accordance with my invention. Such compounds differ from those represented by Formulas A and B in that some of the divalent organic radicals (R in the formulas) have been replaced by monovalent organic radicals, e. g., alkyl, aryl, alkaryl, aralkyl, etc., radicals. Polymers of this type contain the structure a linear polymer incapable of crosslinking, that is, incapable of forming a three-dimensional network, is obtained. In these compounds of silicon with monovalent and divalent organic radicals, the average number of monovalent radicals should not be greater, and preferably is less. than twice the average number of divalent radicals. By proportioning the reactants so that the average number of monovalent radicals is less than twice the average number of divalent radicals. cross-linking can take place during polymerization of the compound to yield a more rigid structure. Illustrative examples of monovalent organic radicals which A in the above formulas may be are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl to octadecyl and higher in the aliphatic series; halogenated and non-halogenated aryl radicals, e. g., phenyl, monoand poly-alkyl phenyl as, for instance, tolyl, xylyl, mono-, diand triethyl phenyl, also naphthyl, alkyl naphthyl (e. g., methyl naphthyl), tetrahydrona-phthyl, anthracyl, benzyl, etc.

Organo-silicon compounds formed of divalent organic radicals linked to silicon (or formed of monovalent and divalent organic radicals linked to silicon) and wherein some of the organic radicals have been replaced by oxygen also may be produced in accordance with this invention. The oxygen-containing compounds are specif ically claimed in my copending application, Serial No. 435,938, filed March 24, 1942, as a division 01 the present application. In such modifications the number of oxygen atoms should not be greater than an average-oi. one ior each two silicon atoms, that is, the number of oxygen atoms should not exceed one-half oxygen per silicon atom. Polymers of this type contain, for example, the structures.

R-i iiR- ietc.

it i I i where A and B have the meanings above given.

Any suitable method may be employed in preparing my new compositions comprising an organo-silicon compound in which a plurality of divalent organic radicals are each linked to two different silicon atoms. For instance, such compounds may be prepared by eflecting reaction between a silicon halide (e. g., silicon tetrachloride, silicon tetrabromide, etc.) and at least two molecular equivalents of the (ii-magnesium derivative of the di-halides (e. g., di-chlorides, di-bromides and di-iodides) of divalent organic radicals such as above named by way of example.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following illustrative examples thereof are given:

Example 1 This example illustrates a method of preparing a polymeric body of the type represented by Formula A and, specifically, Formula F. The

- method of preparation was as follows:

1. One and sixty-five hundredths (1.65) mols of p-dibrombenzene in ether solution was caused to react with 3.45 mols magnesium, resulting in a two-phase system containing 1.32 mols of phenylene (ii-magnesium bromide:

2. The solution of phenylene (ii-magnesium bromide was added slowly, with stirring, to an ether solution of 1.32 mols of silicon tetrachloride and the reaction mixture was heated under reflux for 30 minutes, yielding a phenylene silicon (ii-chloride:

3. One and thirty-two hundredths (1.32) mols of the dimagnesium derivative of mixed isomeric dichlorpentanes in ether solution were then added, with stirring, to the reaction mixture of step 2, and the resulting mass was heated under reflux for 2 hours:

4. The solution of organo-silicon compound was isolated by pouring the entire reaction mass assao'n into water. thereby dissolving out the magnesium salts. Most of the ether was evaporated to yield an extremely viscous, benzene-soluble. yellow resin. Upon evaporation of all the ether there resulated a solid, clear, yellow resin having a nontacky surface.

The product of this example may be described asa reaction product of a silicon halide, specifically silicon tetrachloride, with two molecular equivalents of the di-magnesium derivatives of two organic cit-halides, specifically a di-chloride and a di-bromide.

Example 2 l. The solution of methi phenylene silicon was isolated by pouring the entire reaction mass into water, thereby dissolving out the magnesium salts. The other layer was separated and washed free of magnesium salts. Removal of the ether left a brown, sticky resin which melted at approximately 180 C. It was insoluble in alcohol,

but soluble in benzene and. acetone. Heating for 5 hours at 230 C. did not solidify the molten resin nor cause any apparent physical change.

The product of this example may be described as a reaction product of a silicon halide with one molecular equivalent of the (ii-magnesium derivative' of an organic di-halide and slightly more than two molecular equivalents oi the magnesium derivative of an organic mono-halide.

Example 3 This example illustrates a method of preparing a polymeric body 01' a type similar to hat represented by Formula J. The method of preparation was as follows:

' The first two steps of the process were essentially the same as those described under stem 1 and 2 of Example 1.

3. An ether solution of methyl magnesium bromide containing 1.26 mols methyl magnesium bromide per mol phenyiene silicon dichloride was added slowly, with stirring, to the reaction mass resulting from step 2. The main reaction is:

4. The methyl phenylene silicon chloride was hydrolyzed by pouring the reaction mass on cracked ice:

The ether layer containing the hydrolysis prodnot was separated and washed free of acid. Evaporation of the ether yielded a soft, sticky. yellow, resinous material.

5. The product of step 4 was condensed (dehydrated) by heating the material at a gradually increasing temperature to C. After two hours heating at 110 C. the product was still liquid. but solidified when heated for an additiopai hour at C. This condensation product was a soft, brown resin. It was soluble in benzene, toluene and acetone. This resin became infusible on prolonged heating.

The product of this example may be described as a resinous dehydrated product of hydrolysis of the reaction product of more than one and less than two molecular equivalents of the masnesium .derivative of an organic monohalide, specifically 1.26 mols methyl magnesium bromide, with the product of reaction of a silicon halide with one molecular equivalent of the di-magnesium derivative of an organic di-halide, specifically phenylene di-magnesium di-bromide.

It will be understood, of course, that my invention is not limited to the specific methods shown in the above illustrative examples, nor to the specific reactants and proportions therein shown.

In accordance with this invention chemical compounds consisting of a plurality oi monovalent and divalent organic radicals linked to silicon atoms may be prepared by reacting, for example, a solution of a silicon halide with a solution containing one molecular equivalent of the (ii-magnesium derivative of an organic (ii-halide, reacting the resulting solution of organo-silicon halide with a solution containing two molecular equivalents of the magnesium derivative of an organic mono-halide, and isolating from the reaction mass the organo-silicon compound thereby produced. In preparing compounds of silicon with divalent organic radicals and oxygen, a suitable method, for example, comprises effecting reaction between a silicon halide and more than 1 but less than 2-mo1ecular equivalents of the iii-magnesium derivative of an organic (ii-halide, hydrolyzing the resulting product and dehydrating the hydrolyzed product in the presence or absence of an accelerator of condensation, e. g, a dehydrating agent.

To illustrate how the resinous materials of this invention may be used in industry, the following examples are cited:

A liquid coating composition comprising a volatile solvent and a soluble, heat-hardenable liquid, or a normally solid, resinous polymer, such as above described, is applied to a metallic conductor such as copper wire. Thereafter the coated wire is heated to vaporize the solvent and to harden the polymer. In this way the polymerizetion of the resin may be continued or completed in situ. In manufacturing certain kinds of electrical cables it may be desirable to wrap the conductor with an organic or inorganic fibrous material such as asbestos, glass, cotton or paper before treating it with the liquid resin. A further procedure is to coat and at least partly impregnate the wrapped conductor with the liquid resin, wind the thus insulated conductor into the desired coil, and then heat the wound coil to solidify the resin.

Sheet insulation may be prepared by treating woven or felted organic fabrics or paper with compositions comprising the herein-described resinous materials. Sheet insulation also may be prepared by binding flaky inorganic substances with these new resins. For example, they may be used in the production of laminated mica products comprising mica flakes cemented and bonded together with the polymerized resin. Self-supporting coherent films or sheets Of clay such as bentonite also may be treated to advantage with compositions comprising the polymeric bodies of this invention. Such treated films may be produced as described more fully in, for example, my copending application Serial No. 287,787, filed August 1, 1939.

In addition to their use in the field of insulation, these new resinous compositions also may be used as protective coatings, for instance as coatings for base members such as glass bulbs or other articles of glass, also for coating metals such as iron, steel, copper, etc. They also may be used as sealing compositions, in the production of socalled resistance or semi-conducting paints, and for other commercial applications as described more fully in my copending applications Serial No. 287,787 and 296,819 (filed September 27, 1939) with particular reference to methyl silicones and halogenated aryl silicones.

In certain cases it may be desirable to form mixtures of different polymers of this invention. In other cases, different products capable of being dehydrated or condensed may be mixed and co-condensed to yield resins better adapted for ,a particular application. However, in such cases the components should be mixed before the condensation of the individual materials has advanced to the point where the bodies are incompatible. For other applications it may be desirable to polymerize or condense the liquid resins to solid form and then mix and grind the materials together to form a composite mass.

The polymerizable or the polymerized resins of this invention also may have incorporated therewith various other materials, for example polymerizable or polymerized silicones. Examples of compounds which thus may be used to modify the resins of this invention are those described in my copending applications Serial Nos. 287,787 and 296,819, filed, respectively, August 1 and September 27, 1939, and in applications Serial Nos. 332,097, 332,098 and 332,099 filed April 2'7, 1940,

all of these applications being assigned to the same assignee as the present invention. Thus, polymerizable compositions may be prepared by mixing polymerizable silicones such, for example, as polymerizable methyl silicones, halogenated or non-halogenated aryl silicones, aroxylaryl silicones, methyl aryl silicones, etc., with the herein-described polymers or partial condensation products. The resulting polymerizable mixtures then may be polymerized under heat or under heat and pressure, and in the presence or absence of a polymerization catalyst, to obtain products having properties diflerent from the separately polymerized components. Also, it desired, polymeric silicones such as those mentioned above may be suitably compounded with the polymerizable or polymerized resins 01' this invention. In these and other ways the basic materials of this invention may be modified to provide products having properties best adapted for a particular service application.

The individual, copolymerized or mixed liquid, semi-solid or solid silicon-containing resins of my invention may be suitably incorporated intoother materials to modify the properties of the latter. For example, they may be compounded with sub stances such as natural and synthetic rubber; tars, asphalts and pitches, more specific examples oi which are wood tars, petroleum asphalts and vegetable pitches; natural resins such as wood rosin, copal, shellac, etc.; synthetic resins such as phenol-aldehyde resins, urea-aldehyde resins, modified and unmodified alkyd resins, cumar resins, vinyl resins, esters oi acrylic and methacrylic acids, etc.; cellulosic materials such as cellulose nitrate (pyroxylin), cellulose acetate including the triacetate, cellulose propionate, cellulose butyrate, etc., cellulose ethers such as methyl cellulose, ethyl cellulose, benzyl cellulose, etc. In some cases the hard polymers of this invention may be pulverized and used as fillers for substances such as above mentioned. In other cases,

especially when the silicon resin is compatible with the substance with which it is to be incorporated, it may be in the form of a liquid or relatively soft polymer of low molecular weight prior to compounding with the substance to be modified.

These new silicon resins also may be compounded with various other materials. For example, the hard, brittle polymers may be plasticized by the addition of suitable plasticizing materials or the liquid or low-softening-point polymers themselves may be used as plasticizers 01' other normally brittle substances.

The low molecular weight resinous polymers of this invention also may be dissolved or dispersed in oils, such as linseed oil, China-wood oil, perilla oil, soya bean oil, etc., alone or mixed with solvents, pigments, plasticizers, driers and other compounds of coating compositions to yield products which, when applied to a base member and air-dried or baked, have improved heat resistance.

Laminated products may be made by superimposing organic or inorganic fibrous sheet materials coated and impregnated with these new resins and thereafter bonding the sheets together under heat and pressure. Molding compositions and molded articles also may be formed from these new resins. If desired, filling materials such as asbestos, glass fibers, talc. quartz powder, wood fiour, etc., may be incorporated into such compositions prior to molding. Shaped articles are formed from such compositions under heat or under heat and pressure in accordance with practices now widely used in the plastics arts.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A polymeric chemical compound comprising monovalent saturated aliphatic and divalent aryl radicals linked to silicon atoms, each of a plurality of the divalent aryl radicals being linked to two diflerent silicon atoms.

2. A composition comprising a resinous organo-silicon compound consisting of divalent aryl and saturated aliphatic hydrocarbon radicals linked to silicon atoms, each of a plurality of the divalent aryl radicals being linked to two diilerent silicon atoms.

3. A polymeric compound of silicon and a, di-

valent aryl radical in which the divalent aryl radical links two silicon atoms.

- 4. A polymeric compound of silicon and phenylene radicals in which each of the phenylene radicals links two silicon atoms.

5. A polymeric compound of silicon, phenylene and pentamethylene radicals in which each oi the phenylene radicals links two silicon atoms.

6. The method of preparing an organo-silicon resinous-compound in which a pluralit of divalent aryl radicals are each linked to two separate silicon atom which comprises effecting reaction between a silicon tetrahalide and at least two molecular equivalents of the di-magnesium derivative of a di-halogenated aromatic hydrocarbon.

7. The method of preparing a resinous chemical compound consisting of a plurality of monovalent hydrocarbon radicals and divalent aryl radicals linked to silicon atoms with two difierent silicon atoms linked by divalent hydrocarbon radicals which comprises slowly adding to a solution of a silicon tetrahalide a solution containin one molecular equivalent of the di-magnesium derivative of a di-halogenated aromatic hydrocarbon, reacting the resulting solution of organo-silicon halide with a solution containing two molecular equivalents of the magnesium derivative of mono-halogenated hydrocarbon selected from the class consisting of saturated aliphatic hydrocarbons and aromatic hydrocarbons, and isolating from the reaction mass the organosilicon compound thereby produced.

8. A resinous composition consisting of methyl and phenylene radicals linked to silicon atoms, each of a plurality of the phenylene radicals being linked to two difierent silicon atoms, the average number of methyl radicals being less than twice the average number of divalent radicals.

EUGENE G. ROCHOW.

Patent No. 2,552, 974.

CERTIFICATE OF CORRECTION.

EUGENE G. ROCHOW.

It is hereby certified that error appears in the printed specification of the above numbered'patent requiring correction as follows: Page 1, second column,,1ine k2, forradicals" read -radica1--; line 14.8, for "arkaryl" read -alkaryl--; page 2, first column, line '40, in the formula, .after 'S i" second occurrence, insert a bond; and second column, line 11, after the first formula and before "J" insert --or--; line 16, after the second formula and before "K" insert --or--; page 5, first column, line 55, for

, "methl" read -methyl--; line72, in the formula, for "Si" first occurrence,

read Siand second column, linel'Y, for monohalid'e read --monoha1ide--; page 14., first column, line 55, for "eroxylaryl" read --aroxyaryl-'; page '5, second column, line 2, after "of insert -a-; and that the said Letters Patent should be read with this correction therein that thesame may conform to the record of the case in the Patent Office.

Signed and sealed. this 12th day of September, A. I). 191114..

Leslie Frazer (Seal) Acting Commissioner of Patents.

Patent No. 2,552, 97h.-

CERTIFICA'IPE OF CORRECTION.

EUGENE G. ROCHOW.

It is hereby certified that error appears in the printed specification of the above numbered' patent requiring correction as follows: Page 1, second column, .line 142, for "radicals" read -rsdical--; line 14.8, for "arksryl" "reed --alkaryl--; page 2, first column, line 14.0, in the formula, vafter "'Si" second occurrence, insert a bond; and second column,,line 11, after the first formula and before "J" insert --or--; line 16, after the second formula. and before "K" insert -or-; page 5, first column, line 55, for

v "methl" read --methyl--; line 72, in the formula, for "Si" first occurrence,

reed Siand second column, linel7, for "monohalid'e" read --monohalide--; page 1;, first column, line 55, for "aroxylaryl" read --aroxysryl-'-; page '5, second column, line 2, after f'of" insert -a--; and that the said Letters Patent should be read with this correction therein thst thesame may conform to the record of the case in the Patent Office.

Signed and sealed this 12th day of September, A. D. 191414..

Leslie Frazer (Seal) Acting Commissioner of Patents. 

